Why is phenyl azide so unreactive in [3 + 2] cycloaddition reactions? Demystifying Sustmann's paradigmatic parabola

Vista sencilla de ítem
dc.contributor.authorDomingo, Luis R.
dc.contributor.authorRíos-Gutiérrez, Mar
dc.contributor.authorPérez, Patricia
dc.date.accessioned2025-01-30T19:04:31Z
dc.date.available2025-01-30T19:04:31Z
dc.date.issued2023-09
dc.descriptionIndexación: Scopus
dc.description.abstractThe [3 + 2] cycloaddition (32CA) reactions of phenyl azide with a series of 25 ethylenes of different electronic activation have been studied within Molecular Electron Density Theory (MEDT) at the ωB97X-D/6-311G(d,p) computational level to understand the low reactivity of azides participating in 32CA reactions. Analysis of the reactivity indices allows characterizing phenyl azide as a moderate electrophile and a moderate nucleophile. The relative reaction rate constants kr of twelve selected 32CA reactions, together with the electrophilicity ω and nucleophilicity N indices of the corresponding ethylenes, allow us to classify these 32CA reactions into four groups: (i) group A, involving supernucleophilic ethylenes and displaying a kr > 104; (ii) group B, involving strained cyclic ethylenes and displaying a kr < 102; (iii) group C, involving strongly electrophilic ethylenes and displaying a kr ≤ 102, and (iv) group D, involving moderately electrophilic and nucleophilic ethylenes and displaying a kr < 2. These four groups are characterized in Sustmann's “parabolic correlation”, which results from an inaccurate interpretation of the reactivity of phenyl azide, which is not an “ambiphilic species” but rather a moderate electrophile that reacts efficiently only with supernucleophilic ethylenes in reverse electron density flux (REDF) zw-type 32CA reactions. © 2023 The Royal Society of Chemistry.
dc.description.urihttps://pubs.rsc.org/en/content/articlelanding/2023/qo/d3qo00811h
dc.identifier.citationOrganic Chemistry Frontiers. Volume 10, Issue 22, Pages 5579 - 5591. 26 September 2023
dc.identifier.doi10.1039/d3qo00811h
dc.identifier.issn2052-4110
dc.identifier.urihttps://repositorio.unab.cl/handle/ria/63355
dc.language.isoen
dc.publisherRoyal Society of Chemistry
dc.rights.licenseAttribution 3.0 Unported Deed (CC BY 3.0)
dc.rights.urihttps://creativecommons.org/licenses/by/3.0/
dc.subjectCarrier Concentration
dc.subjectComputation Theory
dc.subjectCycloaddition
dc.subjectElectron Density Measurement
dc.subjectMolecular Electron Density Theory (MEDT)
dc.titleWhy is phenyl azide so unreactive in [3 + 2] cycloaddition reactions? Demystifying Sustmann's paradigmatic parabola
dc.title.alternative
dc.typeArtículo
Archivos
Bloque original
Mostrando 1 - 1 de 1
No hay miniatura disponible
Nombre:
d3qo00811h.pdf
Tamaño:
1.17 MB
Formato:
Adobe Portable Document Format
Descripción:
TEXTO COMPLETO EN INGLÉS
Descargar
Bloque de licencias
Mostrando 1 - 1 de 1
No hay miniatura disponible
Nombre:
license.txt
Tamaño:
1.71 KB
Formato:
Item-specific license agreed upon to submission
Descripción:
Descargar
Colecciones
FCE - Artículos de Revista